Process for producing stabilized high strength urea-aldehyde insulating foams

ABSTRACT

A process for producing stable urea-aldehyde polymers with high structural strength from two storable liquid ingredients. In this process, partially cured liquid urea-formaldehyde resin is reacted with an aqueous cross-linking solution comprising one or more alkyl or aryl dialdehydes containing two to eight molecular carbons and the hydrogen ion concentration needed to catalyze the completion of the reaction of the dialdehydes and the urea-formaldehyde. The process for producing urea-aldehyde polymers, having improved structural strength and reduced aldehyde vapor emission during their production and prolonged use, is especially effective for manufacturing products for the building industry, such as urea-aldehyde insulating foam, wood-filled particle board, and plywood. The increased polymer strength and the elimination of the hazardous and objectionable aldehyde odor is achieved by maintaining the molecular ratio of total aldehyde moieties to urea to about 1.8 and the molecular ratio of the aldehyde moieties in the dialdehydes to those in formaldehyde at about 0.2. The process requires that the dialdehydes be substantially contained in the cross-linking solution for system storability and long term reactivity. The hydrogen ion concentration required in the cross-linking solution is represented by a pH of about 3 and may be achieved by addition of water soluble acid or by heating the mixture and converting some aldehydes to acids.

This is a division, of application Ser. No. 836,492, filed Sept. 26,1977, now U.S. Pat. No. 4,097,419.

BACKGROUND OF THE INVENTION

This invention relates to urea-aldehyde polymers and more particularlyto a process for producing polymers, having properties of highstructural strength and low residual aldehyde vapor, by the reaction oftwo storable solutions comprising partially cured aqueousurea-formaldehyde resin and aqueous dialdehyde cross-linking solution.The process for producing the new polymers is particularly useful in themanufacture of high strength, low odor, urea-aldehyde insulating foam,and high strength, low odor particle board and plywood.

The building industry consumes large amounts of urea-formaldehydepolymers in the manufacture of structural, decorative, and insulatingboards, and in lightweight insulating foam. Urea-formaldehyde polymershave been particularly important because they may be formed and cured inrelatively simple and economical procedures, and because they may becombined with other low cost materials, particularly cellulosic fibersand wood, to form composites which are economically useful buildingmaterials.

Urea-formaldehyde polymers developed to date have not had the structuralstrength required to produce an effective foam insulation or compositestructural board, which would not generate objectionable and unhealthyamounts of formaldehyde vapor during the formation and service life ofthe products. Copending U.S. application Ser. No. 761,321, by thisinventor, disclosed improvement in the chemical stability ofurea-formaldehyde foam by reaction of 1-5% of dialdehydes, containingtwo to six molecular carbons, and additional urea, in the preparation ofa partially cured resin for use in insulating foam manufacture. Althoughthe said disclosure represented an advance in the art of producinginsulating foams having properties of long term stability, it did notprovide a process for the production of polymers with added structuralstrength required to provide load bearing properties or stiffness tobuilding structural members. Some such structural members used forbuilding include core fillings for thin-skin wall panels or door cores.More conventional structural uses include resin-filled chip or cellulosefiber panels. Further, the said disclosure did not provide a system inwhich the ingredient liquids are storable for practical periods of timenor a system which could be practically applied to the manufacture ofcomposite boards and plywood. The partially cured resin containing 1 to5 percent dialdehyde and added free urea must be used within a few daysof its manufacture to prevent the precipitation of an insolubleglyoxal-urea-urea-formaldehyde copolymer and deactivation of thepartially cured resin.

Because of the realization of possible hazards from the continuedevolution of formaldehyde from particle boards, plywood, and insulatingfoams, and interest by governmental regulatory agencies, there has beenconsiderable evidence of progress in the art. Kawashima in Japanese Pat.No. 74 71,118 discloses the use of large amounts of calciumlignosulfonate to reduce free formaldehyde in luan plywood. The presenceof large amounts of base-forming materials such as calcium, sodium,potassium, ammonia, or urea does reduce initial free formaldehydecontent of the product but weakens rather than strengthens the finalproduct. Dashkovskaya et al in USSR Pat. No. 480,555, Aug. 15, 1975disclose that the addition of mineral oil containing sodium silicatereduced formaldehyde odor in particle board as produced. However, sodiumsilicate after heating and drying gives a basic reaction, so thatrepeated moistening and drying of the particle board in structuralservice will degrade and not strengthen the urea-formaldehyde polymer.

It is therefore a primary object of this invention to provide a processfor producing from two storable liquids stable urea-aldehyde polymershaving the structural strength required for use in structural membersfor the building industry.

It is another object of this invention to provide a process forproducing urea-aldehyde polymers having high structural strength withthe elimination of objectionable formaldehyde vapor emission during thepolymer service life.

It is another object of this invention to provide a process forproducing urea-aldehyde polymers from a partially curedurea-formaldehyde resin solution and a cross-linking solution, both saidsolutions having commercially acceptable storage life properties.

It is another object of this invention to provide a process forproducing urea-aldehyde insulating foams having properties of increasedstructural strength and decreased formaldehyde vapor emission.

It is another object of this invention to provide a process forproducing urea-aldehyde polymer-filled particle board having propertiesof increased structural strength and decreased formaldehyde vaporemission during the formation and service life of the board.

It is another object of this invention to provide a process forproducing thin-skin foam filled building panels suitable for use incommercial construction applications.

These and other objects will be evident from the following descriptionof the invention.

SUMMARY OF THE INVENTION

It has now been discovered that the foregoing objects can beaccomplished, and stable urea-aldehyde polymers produced, havingproperties of increased structural strength and decreased formaldehydeodor emission, by a process for the reaction of separately storedsolutions of partially cured urea-formaldehyde resin and ofcross-linking agent, comprising one or more alkyl or aryl dialdehydescontaining 2 to 8 molecular carbons, as catalyzed by increased hydrogenion concentrations represented by pH between 2 and 5. Surprisingly, thehigh ratio of aldehyde moieties to urea which are required to producepolymers having high structural strength may be used without the hazardfrom objectionable aldehyde vapor, during the formation and service lifeof the polymer, when twenty percent of the total aldehyde moieties arepresent as alkyl or aryl dialdehydes having 2 to 8 molecular carbons andthe said dialdehydes are provided as a cross-linking solution at thetime of the final polymer formation and cure.

The term aldehyde moiety is used in this disclosure to mean a carbonylgroup functioning chemically as an aldehyde. A molecule of glyoxalcontains two aldehyde moieties and a molecule of formaldehyde containsonly one. The term cross-linking solution is used herein to denote asolution of dialdehyde which has two aldehyde moieties and which canreact with partially cured urea-formaldehyde resin, urea, andformaldehyde to link them into longer chain molecules through thedialdehyde acting as a bridge.

DESCRIPTION OF THE INVENTION

A process has been discovered for the reaction of separately storedsolutions of partially cured urea-formaldehyde resin and cross-linkingagent which produces polymers having structural strength suitable foruse in the building industry and which surprisingly, may be used in apractical manner without the hazard from objectionable vapor. Thepolymers produced by the process of this invention may be used in avariety of uses for which urea-aldehyde polymers are normally appliedwhere long term strength and low odor are required, particularly for themanufacture of urea-aldehyde insulating foams, and resin filled particleboard and plywood. The polymers produced by the process of thisinvention may be used with or without the addition of fillers, such ascolloidal silica, bagasse, attapulgite clay, wood chips, wood fiber,cellulose products or lignin. To achieve the structural strength and lowaldehyde vapor emission from the urea-aldehyde, the process I havediscovered must be closely and accurately followed.

The cross-linking solution must contain water soluble alkyl or aryldialdehydes containing 2 to 8 molecular carbons. Glyoxal is the mosteconomical and most reactive of the dialdehydes and is generallypreferred for most urea-aldehyde polymers. The dialdehydes with longerskeletal claims such as suberic aldehyde impart additional flexibilityto the cured products.

It is critical that the dialdehydes used for cross-linking andstrengthening the urea-aldehyde polymers be stored separate from thepartially cured urea-formaldehyde resin until cure of the polymer isinitiated by acid catalysis. The presence of appreciable amounts of thedialdehydes in the partially cured urea-formaldehyde resin results inreaction of the dialdehyde with the urea-formaldehyde resin which withinseveral days causes precipitation and deactivation of the resin.

For satisfactory performance of the process, it is necessary that themolecular ratio of aldehyde moieties to formaldehyde in the polymer becontrolled between 0.1 and 1.0, and preferably between 0.2 and 0.4. Whenthe aldehyde moieties from dialdehyde were lower than 0.1 theformaldehyde vapor emission from polymers was excessive, and thestructural strength was reduced significantly where polymers containedappreciably more than 0.4 aldehyde moieties per mol of formaldehyde.

Increased urea-aldehyde structural strength was found at total aldehydemoieties to urea molecular ratios of between 1.6 and 2.2, and maximumstructural strength was found between the ratios of 1.7 and 2.0.

The polymer cure must be catalyzed by acid conditions in the pH rangebetween 2 and 5. The acidity for the polymer cure may be derived fromorganic or mineral acids such as formic, phosphoric, or sulfuric acidsadded to the cross-linking agent, which may also contain a surfactant,for example, in the production of urea-aldehyde insulating foam. Theacidity for the polymer cure may also be derived by heating thepartially cured resin to form formic acid by the Cannizaro reaction, inthe production of particle board. Where rapid in-situ cure at ambienttemperature is desired, pH of polymer mixture should be brought to 2-3.

The properties of the partially cured urea-formaldehyde resin used inthe process of this invention must be closely controlled to obtain apolymer with high structural strength and low aldehyde vapor emission.The said resin must have a total solids content in water amounting to 40to 65 percent and have a formaldehyde to urea mol ratio of 1.2 to 1.7.To achieve maximum strength with minimum free formaldehyde, I prefer thepartially cured urea-formaldehyde resin to contain 45 to 52 totalpercent solids and a formaldehyde to urea mol ratio of 1.3 to 1.5. Thepartially cured urea-formaldehyde resin may contain additives to modifythe final product, so long as the additives do not interfere with thedialdehyde reaction. For example, polyhydroxy type humectants, such asdipropylene glycol, sorbitol or polyethylene glycol may be readily usedin resins for foam production. Blended urea-formaldehyde andmelamine-formaldehyde resins may also be used in the production ofpolymer-filled particle board.

The partially cured urea-formaldehyde resins found optimum for use withthe dialdehyde cross-linking agents are cooked at 98° to 103° C. at pH5.4 to 5.6 until viscosity reaches 20 to 40 centistokes at 30° C. andthen neutralized to pH 7.2 to 7.6.

The concentration of the dialdehyde in the cross-linking solution is notcritical to the formation of urea-aldehyde polymers with high structuralstrength and low free formaldehyde so long as the ratio of dialdehyde toformaldehyde and the ratio of total aldehyde moieties to urea are heldin the critically important process ranges defined above. It isnecessary to the process that the cross-linking and partially curedresin solutions be rapidly and completely blended so that the curedpolymer has a constant molecular ratio throughout.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The following examples illustrate the effectiveness and limits of thenew process for producing stable urea-aldehyde polymers having highstructural strength, low odor, and long term storability of ingredients.All parts and percentages are by weight unless otherwise specified.

EXAMPLE 1

A partially cured aqueous-urea-formaldehyde resin was prepared by addingat ambient temperature to a closed, stirred, jacketed, stainless steelreactor, fitted with internal cooling coils, the following ingredients:5062 parts water, 6680 parts prilled urea (46% N, coated with trace offormaldehyde), 1850 parts 70% aqueous sorbitol, and 13875 parts 50%aqueous low buffer uninhibited formaldehyde.

The mixture was agitated vigorously and circulated through an externalcentrifugal pump and low pressure (7 psig) steam was applied to thejacket to increase temperature to 98° C. at pH 7.2. When the temperaturereached 98° C., 20% aqueous formic acid was added to decrease the pH inthe clear solution to 5.3. Steam was removed from the jacket and coolingwater was circulated through the internal coils of the reactor to holdthe temperature to 103° C. maximum. Temperature was then regulated byuse of steam and cooling water as required. The pH was held in the rangeof 5.3 to 5.6 until a dilution cloud point test was obtained at 2.5 to 1water dilution. When the desired partial cure of the urea-formaldehyderesin was indicated by the dilution test after 35 minutes at 98° to 103°C., maximum cooling was applied in the internal coils and temperaturewas decreased to 50° C. To the agitated clear solution at 60° C. wasadded the following: 6360 parts water and 3598 parts prilled urea.Agitation was continued for 20 minutes while the still clear solutionwas cooled to ambient temperature by cooling water in the internalcoils. The reaction mixture was then neutralized to pH 7.4 by theaddition of triethanolamine. To the agitated neutralized partially curedresin was added the following: 1000 parts dipropylene glycol, 400 partsfurfuryl alcohol, and 205 parts methanol. The partially curedurea-formaldehyde resin was then stored in drums for subsequent use. Themol ratio of formaldehyde to urea was 1.31 and calculated total solidscontent was 50.7%.

A cross-linking solution was prepared in polyethylene-lined drums with55 gallons capacity by adding the following ingredients: 50 parts 40%aqueous glyoxal, 7.5 parts dibutyl naphthalene sulfonic acid, 5.5 partsorthophosphoric acid, 5.6 parts oxalic acid, and 497.0 parts of water.The ingredients were completely mixed and stored for subsequent use inproducing foam.

The partially cured urea-formaldehyde resin and the aqueouscross-linking solutions were separately supplied continuously bydiaphragm pumps to a commercial urea-formaldehyde foam machine where thecross-linking solution was converted to a froth by commingling with airin a glass tube 2 inches in diameter and 4 inches long, filled withglass beads 1/4 inch in diameter. The partially cured urea-formaldehyderesin was added to the frothed cross-linking solution as a liquidthrough a 1/4 inch inside diameter tube located in the center of the 2inch tube where the frothed cross-linking solution is discharged fromthe frother to a 1 inch diameter by 6 feet long curing-application hose.The feed rates measured to the foam machine were as follows: air, 2.5cubic feet per minute (at 25° C. and 760 mm Hg absolute); cross-linkingsolution, 1.18 pounds per minute; and partially cured resin, 0.97 poundsper minute.

The blended foam left the curing-dispensing hose in a continuous streamand was used to form contiguous masses of urea-aldehyde insulation. Testcubes measuring 4 inches on each side were cut from the insulation masswithin one minute of application and properties of these cubesdetermined when sampled and after they had completely dried. Themolecular ratio of total aldehyde moieties to urea was 1.69 and themolecular ratio of glyoxal aldehyde moieties to formaldehyde was 0.246.Density of the wet foam cube was measured to be 2.35 pounds per cubicfoot. The foam had the strength to support itself in 30 seconds andgained stuctural strength as it cured. The test cubes were stored underambient room conditions and were weighed each day to determine dryness.After 10 days storage, weight was stable indicating the test cubes to bedry. Density of the test cubes was measured and found to be 0.65 poundsper cubic feet.

Structural strength of the test cubes was measured by placing a testcube on a platform scale, covering the cube with a 4 inch square steelplate and applying weight downwardly onto the plate and thus evenly tothe surface of the cube. Weight was applied in increasing amounts untilthe cube lost its ability to support the force, and collapsed to 75% orless of its original volume. The exact weight required was thenrecorded. The weight recorded as the yield point for the foam was theaverage of the weight required for collapse on the three separate faces.There was little difference in the yield point of the three faces of thetest cubes. The yield point was 2.6 pounds per square inch.

EXAMPLE 2

A series of foams was prepared by the method of example 1 using thepartially cured urea-formaldehyde resin as example 1 and varying theglyoxal concentration in the cross-linking solution. The density of thefoams produced were maintained about constant by controlling the amountof air supplied to the system, and the weight ratio of partially curedresin to cross-linking solution was maintained at about 0.9. Samplecubes were recovered from the contiguous masses of wet foam produced.These cubes were dried and tested for structural strength by the yieldpoint method described in example 1. The results of these evaluationsare listed as follows:

    ______________________________________                                                              Ratio                                                                Ratio    Aldehyde                                                             Aldehyde Moieties  Yield                                              Dry     Moieties in Glyoxal to                                                                           Point                                              Den-    to Urea  Aldehyde  of                                            Test sity    Mole-    Moieties in                                                                             Foam                                          No.  lbs/ft..sup.3                                                                         cules    Formaldehyde                                                                            lbs/In.sup.2                                                                        Comments                                ______________________________________                                        1    0.68    1.48     0.0       0.7   Soft, chalky                            2    0.65    1.70     0.205     1.8   Hard, -     lustrous                    3    0.64    2.11     0.410     2.2   Hard, -     lustrous                                                          surface                                 4    0.67    2.36     0.595     1.0   Friable                                 5    0.76    2.70     0.794     0.7   Very friable                            ______________________________________                                    

EXAMPLE 3

A series of foams was prepared by the method of example 1 using thepartially cured resin of example 1 and varying the glyoxal concentrationin the cross-linking solution. The density of the foams was increased byreducing the amount of air below that used in example 2. The weightratio of partially cured resin to cross-linking agent was maintained atabout 1.0. Sample cubes were evaluated as in example 2. The results ofthese evaluations are listed as follows:

    ______________________________________                                                                  Ratio                                                                         Aldehyde                                                            Ratio     Moieties                                                            Aldehyde  in Glyoxal to                                             Dry       Moieties to                                                                             Aldehyde   Yield Point                              Test  Density   Urea      Moieties in                                                                              of Foam                                  No.   lbs/ft.sup.3                                                                            Molecules Formaldehyde                                                                             lbs/In.sup.2                             ______________________________________                                        1     1.07      1.48      0.0        1.2                                      2     0.98      1.69      0.253      2.4                                      3     1.05      1.85      0.372      2.9                                      4     1.11      2.42      0.794      0.8                                      ______________________________________                                    

EXAMPLE 4

A partially cured urea-formaldehyde resin was prepared by the method ofexample 1, and at the completion of the preparation, 40% aqueous glyoxalwas added in the amount of 0.20 aldehyde moieties per mol offormaldehyde in the resin. The cross-linking solution was made by themethod of example 1, except that no dialdehyde was added. A foam wasprepared by the method of example 1 the day following the preparation ofthe partially cured resin. The yield point of this foam was 1.0 poundsper square inch compared to 1.8 pounds per square inch for the productof example 1. The partially cured resin was stored at ambienttemperature for 7 days, and used to produce foam again by the method ofexample 1. The foam collapsed and would not harden without the additionof large amounts of acid to the cross-linking solution. Foams producedfrom the stored resin using the acid required for hardening were highlyfriable, low in structural strength, and generally unsuitable for use.Inspection of the resin showed that the glyoxal had reacted with thepartially cured urea-formaldehyde resin during storage to deactivate itand had caused precipitation of some of the urea-aldehyde polymer.

In a comparative test, using the foaming system of example 1 where theglyoxal was added to the cross-linking solution, the partially curedurea-formaldehyde solution and the cross-linking solution were storedseparately for 90 days at ambient temperature. These ingredients werethen foamed by the method, conditions, and ratios of example 1. Dry foamdensity was 0.63 pounds per cubic foot, and structural strength wasindicated by an average yield point measurement of 1.8 pounds per squareinch.

EXAMPLE 5

A sample of the urea-aldehyde foam from example 1 was cut into a cubehaving 4 inch sides and dried for 5 days at ambient temperatures, ofabout 20° to 25° C., and then placed in a closed glass container fittedwith nozzles for the introduction and discharge of air streams. Air waspassed at a rate of 10 milliliters per minute over the test foam cubeafter first passing through a Haberman type bubbler containing a smallamount of distilled water at ambient temperature. The air leaving thetest cube was passed through another Haberman bubbler containing 50 mlof 1 percent aqueous hydroxylamine hydrochloride to absorb any aldehydecarried from the test cube, convert the aldehyde to the correspondingoxime and produce an equivalent amount of free hydrochloric acid. Thepassage of air over the test block and through a parallel blank system,was continued for 7 days. The test and blank hydroxylamine solutionswere then titrated with 0.05 normal potassium hydroxide to determinehydrochloric acid liberated and from that number, the amount ofaldehyde, as formaldehyde, which was stripped from the test foam cube.The aldehyde recovered was about 0.1 milligram, amounting to 1 ppm orless aldehyde concentration in the total air passed over the cube in thetest.

Another test cube was made by the procedure of example 1 except that theglyoxal content was replaced by an equal amount of formaldehyde. The 7day air passage test showed that 1.44 milligrams of aldehyde, asformaldehyde, was removed from the test cube, indicating an averagealdehyde concentration in the air of slightly more than 10 parts permillion.

EXAMPLE 6

To a 4-liter capacity beaker was added 40 grams of cross-linkingsolution having the following composition:

    ______________________________________                                        Component                   Wt %                                              ______________________________________                                        Suberic Aldehyde            6.5                                               Nacconal SZA (80% alkyl benzene sulfonic acid)                                                            2.0                                               Sulfuric Acid               0.6                                               Water                       90.9                                              ______________________________________                                    

The cross-linking solution was beat to a light froth using a kitchentype blender set on high speed, and the blender was then set to mediumspeed. To the frothed cross-linking solution was slowly added 30 gramsof the partially cured urea-formaldehyde resin from example 1. Mediumspeed blending was continued for 15 seconds after the resin addition andthe blender was withdrawn from the foam. Molecular ratio of totalaldehyde moieties to urea was 1.65 and ratio of aldehyde moieties insuberic aldehyde to formaldehyde was 0.21.

The foam was set to the point of self support in the beaker within 45seconds. The foam remained in the beaker for 7 days to complete curing.The foam sample was then removed from the beaker and allowed to dry for7 days at ambient room conditions. Density of the dried foam sample was1.12 pounds per cubic foot. Yield point of the foam was 2.7 pounds persquare inch and the foam was somewhat more flexible than the product ofexample 1.

EXAMPLE 7

A partially cured aqueous urea-formaldehyde resin was prepared by addingat ambient temperature to a closed, stirred, jacketed glass round bottomflask, fitted with a reflux condenser, and having 2 liters volumecapacity, the following ingredients: 340 grams water, 412 grams crystalurea, and 695 grams 50% aqueous uninhibited formaldehyde. The mixturewas heated to 97° C. at pH 7.4 and treated with dilute formic acid todecrease pH to 5.8, and temperature rose to 100° C. and then heldbetween 94° and 100° C. for 30 minutes. The temperature was decreased to55° C. and the following ingredients were added: 100 grams water and 53grams urea with continued agitation. The mixture was neutralized to pH7.1 by addition of triethanolamine and cooled to ambient temperaturewhile continuing the agitation. Chemical solids calculated were 50.8%,and formaldehyde to urea molecular ratio was 1.5.

A cross-linking solution was prepared by adding 2 grams of ammoniumchloride catalyst to 100 grams 40% aqueous glyoxal solution.

The partially cured resin was thoroughly blended with a mixture ofhardwood chips passing a Tyler 3 mesh screen, to give a mixturecontaining 10% partially cured urea-formaldehyde resin. This mixture wasformed into three mats which were then sprayed evenly with thecross-linking solution amounting to 13.2% of the urea-formaldehyde resinon the hardwood chips. The molecular ratio of glyoxal, as aldehydemoieties, to formaldehyde was 0.24 and the molecular ratio of totalaldehyde moieties to urea was 1.85.

The treated mat of mixed hardwood chips was then pressed at 350 poundsper square inch pressure and 160° C. for 45 minutes. The cure was haltedon one of the mats after 10 minutes at 160° C., and 20 grams of the matmaterial was removed and stirred into 100 ml distilled water. pH wasdetermined to be 4.5 on that sample. Strong, hard surfaced particleboards were obtained with the other two mats. Free formaldehyde analysisshowed less than 1 part per million in both boards.

EXAMPLE 8

A partially cured urea-formaldehyde foam resin was prepared by themethod of example 7 to the same 1.85 overall aldehyde moiety ratio. Nocross-linking solution was sprayed on the mat of mixed hardwood chipsbefore pressing. Objectionable formaldehyde odor was emitted from thepress during the preparation of the board at the same conditions ofexample 7. Free formaldehyde analysis of the completed board showed 35parts per million.

EXAMPLE 9

A contiguous mass of the foam produced in example 1, was pumped directlyfrom the foam blending machine into vented hollow rectangular panels 8feet long, 4 feet wide, and 2 inches deep, composed of aluminum sheets1/16 inch thick tacked over a perimeter frame of 2 inch by 2 inch pineboards. After curing and drying for 10 days the panels were rigid enoughfor use as an outside wall surface on a utility building. Density of thedry foam in the panels was found to be 0.87 pounds per cubic foot.

The same type of operation was used to apply the foam of example 1filling hollow core interior doors. The foam increased the soundresistance and the stiffness of the door significantly from that of theregular "egg crate" cardboard filled doors made with 1/4 inch thick woodskins.

I claim: .[.1. An improved process for producing stable urea-aldehydeinsulating foams having properties of improved structural strength andlow formaldehyde vapor emission, from two separate storable liquids,said process comprising: blending an air-foamed solution containingdialdehydes having two to eight molecular carbons, surfactant, andmineral acid, with a partially cured aqueous urea-formaldehyde resincontaining between 1.3 and 1.5 mols of formaldehyde per mol of urea andabout 50 percent total solids, so that the molecular aldehyde moietiessupplied by the dialdehyde are between 0.2 and 0.4 times the number ofaldehyde moieties supplied by formaldehyde, and the molecular ratio oftotal aldehyde moieties to urea is between 1.7 and 2.0; curing anddrying the blended fluids at a pH between 2.0 and 3.5 at ambientconditions until the foam hardens..]. .[.2. The process of claim 1wherein dipropylene glycol, sorbitol, or polyethylene glycols, are addedto the partially cured resin solution..]. .[.3. The process of claim 1wherein attapulgite clay, or colloidal silica are added to the aqueousdialdehyde solution..]. .[.4. The process of claim 1 wherein the blendedurea-aldehyde foam is applied as contiguous mass into a thin-skinnedcontainer to harden into a structural member..]..Iadd.
 5. An improvedprocess for producing stable urea-aldehyde polymers, having propertiesof high structural strength and low free formaldehyde content, from twoseparate storable fluids, said process comprising: blending aqueousalkyl or aryl, dialdehydes containing between two and eight molecularcarbons with partially cured aqueous urea-formaldehyde resin, containingbetween 1.2 and 1.7 mols of formaldehyde per mol of urea and about 50percent total solids, so that the molecular aldehyde moieties suppliedby the dialdehydes are between 0.1 and 1.0 times the number of aldehydemoieties supplied by formaldehyde, and the molecular ratio of totalaldehyde moieties to urea is between 1.6 and 2.2; and curing and dryingthe blended fluids at a pH between 2 and 5 until the polymer hardens..Iaddend. .Iadd.
 6. An improved process for producing stableurea-aldehyde polymers, having properties of high structural strengthand low free formaldehyde content, from two separate storable fluids,said process comprising: blending aqueous alkyl dialdehydes containingbetween two and eight molecular carbons with partially cured aqueousurea-formaldehyde resin containing between 1.3 and 1.5 mols offormaldehyde per mol of urea and about 50 percent total solids, so thatthe molecular aldehyde moieties supplied by the dialdehyde are between0.2 and 0.4 times the number of aldehyde moieties supplied byformaldehyde, and the molecular ratio of total aldehyde moieties to ureais between 1.7 and 2.0; and curing and drying the blended fluids at a pHbetween 2 and 5 until the polymer hardens. .Iaddend..Iadd.
 7. Theprocess of claim 6 wherein the alkyl dialdehyde is glyoxal, and, or,suberic aldehyde. .Iaddend..Iadd.
 8. An improved process for producingstable urea-aldehyde polymer filled wood particle board havingproperties of increased structural strength and decreased freeformaldehyde from two separate storage liquids, said process comprising:blending one part partially cured aqueous urea-formaldehyde resincontaining between 1.3 and 1.5 mols of formaldehyde per mol of urea andabout 50 percent total solids, with between 6 and 12 parts finelydivided wood particles; evenly spraying the blended wood particles withan aqueous solution containing alkyl dialdehydes having between two andeight molecular carbons so that the molecular aldehyde moieties suppliedby the dialdehyde are between 0.2 and 0.4 times the number of aldehydemoieties supplied by formaldehyde, and the molecular ratio of totalaldehyde moieties to urea is between 1.7 and 2.0; and curing and dryingby heating and pressing the total mixture to a temperature between 120°and 180° C. for 3 to 45 minutes, at pressures between 50 and 500 poundsper square inch, so that pH is reduced to about 5 during the cure..Iaddend.